WO2007132032A1 - Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus - Google Patents

Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus Download PDF

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Publication number
WO2007132032A1
WO2007132032A1 PCT/ES2006/070055 ES2006070055W WO2007132032A1 WO 2007132032 A1 WO2007132032 A1 WO 2007132032A1 ES 2006070055 W ES2006070055 W ES 2006070055W WO 2007132032 A1 WO2007132032 A1 WO 2007132032A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron
nitrogen
sulfate
fertilizer
fertilizers
Prior art date
Application number
PCT/ES2006/070055
Other languages
English (en)
Spanish (es)
Inventor
Sergio Atares Real
Original Assignee
Iniciativas Agroindustriales De Teruel, S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Iniciativas Agroindustriales De Teruel, S.L. filed Critical Iniciativas Agroindustriales De Teruel, S.L.
Priority to ES06743493T priority Critical patent/ES2398234T3/es
Priority to PCT/ES2006/070055 priority patent/WO2007132032A1/fr
Priority to EP06743493A priority patent/EP2017242B1/fr
Publication of WO2007132032A1 publication Critical patent/WO2007132032A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes

Definitions

  • the present invention relates to a process for obtaining nitrogenous and complex fertilizers, which contain in their composition a nitrification inhibitor, the inhibitor has as an active principle the presence of a reducing cation, in particular iron II from by-products of the titanium industry.
  • the invention also relates to the fertilizers thus obtained.
  • the N applied to the soil through fertilizers has different forms, mainly nitric, ammoniacal, ureic and organic.
  • This N once applied to the soil undergoes transformation processes that convert some forms into others, producing absorption by crops, or loss of the nutrient in different forms: loss by atmospheric emissions of nitrogen oxides and ammonia . (By known processes as volatilization and denitrification). loss from leaching processes, loss due to soil erosion.
  • N as a source of nutrients is inevitable, and therefore what must be done is to find the best way to apply it and reduce the processes of nitrogen loss by the different processes that occur in the soil.
  • the key idea is to increase the efficiency in the use of nitrogen, this concept has the direct consequence of reducing the amount of nitrogen applied per unit of food produced.
  • the fertilizer of the present invention is embedded in high efficiency fertilizers that are defined as products with characteristics that minimize the potential for nutrient losses to the environment.
  • Fertilizers of controlled release Fertilizers gradual release. Stabilized fertilizers (those containing urease or nitrification inhibitors).
  • Stabilized fertilizers have two types of inhibitors:
  • the stabilized fertilizers to which the fertilizer described in patent ES2204307 belongs, are so far the most widespread, and have been developed mainly to control the nitrification process.
  • Nitrification is an aerobic oxidation process of reduced forms of nitrogen (ammonia) to nitrites and nitrates, by autotrophic or heterotrophic routes. The most widespread is the autrotrophic form that is developed by the Nitrosomas and Nitrobacter bacteria. The inhibitors that exist to date interact with the Nitrosomes and prevent the transformation of ammoniacal to nitrite, therefore the ammoniacal form is stabilized, which is more stable to leaching and denitrification.
  • ammonia nitrogen
  • nitrification inhibitors have been developed but to date only three of them have had any success in their application, and have been recognized as nitrification inhibiting agents by European regulatory bodies, nitropyrine, dicyandiamide, and BASF has recently developed DMPP recently (3,4, dimethyl pyrazole phosphate).
  • the purpose of the following patent is to provide nitrogen efficiency fertilizer formulations of improved efficiency and its production method to achieve fertilizers that maintain in the soil the most stable and efficient forms of fertilization that is ammoniacal nitrogen and urea using substances that are they usually occur on the ground in a natural way.
  • the nitrogen fertilizer object of the invention has as basic raw materials compounds of reduced nitrogen.
  • ammonia and the reaction products of this substance in ammoniacal and ureic forms not including the presence of nitrogen oxides. They are mainly urea, ammonium sulfate and ammonia, although no other source of these forms is ruled out.
  • a second basic material of this fertilizer is a stable compound of iron (II).
  • Fe (II) is a known reducing agent.
  • This cation is capable of capturing oxygen from the soil to pass from Fe 2+ to Fe 3+ , so this oxygen is not available for the activity of nitrifying bacteria, therefore by decreasing oxidation activity, and More stable ammoniacal form is maintained for longer.
  • the process starts from an iron (II) salt, mainly from byproducts of TiO ⁇ production from Ilmenite or from Titanium Slags, these by-products are mainly iron sulfates with a high amount of free sulfuric acid (to avoid oxidation to Fe 3+ ), such as iron sulfate heptahydrate also known as caparrosa, and a byproduct based on iron (II) sulfate monohydrate, the free acid content ranges from 2 to 40%.
  • iron (II) salt mainly from byproducts of TiO ⁇ production from Ilmenite or from Titanium Slags
  • these by-products are mainly iron sulfates with a high amount of free sulfuric acid (to avoid oxidation to Fe 3+ ), such as iron sulfate heptahydrate also known as caparrosa, and a byproduct based on iron (II) sulfate monohydrate, the free acid content ranges from 2 to 40%.
  • iron salts have to be maintained maximum possible time in this active form as iron (II), however it is not possible to handle a fertilizer product with free acidity since this would cause caking phenomena and reactions with other substances causing adverse phenomena for the quality of the final product.
  • the stabilization method at higher pH values of the order of 5 and 6 should be sought.
  • the transformation of iron (II) sulfate to ferrous ammonium sulfate hexahydrate (SAFH) is carried out, which is much more stable to oxidation at typical pH values of the final product of fertilizers.
  • the fertilizer of the invention comprises ferrous ammonium sulfate hexahydrate that sequesters the oxygen present in the soil, reducing the oxidative activity of nitrifying bacteria.
  • a complex fertilizer can be obtained by adding other raw materials in the granulation stage that provide the characteristic nutrients of this type of formulations, such as monoammonium phosphate, diammonium phosphate, TSP (Triple super phosphate), SSP (Simple super phosphate), phosphate rock, potassium chloride, potassium sulfate.
  • the process has a first stage of mixing in a pug-mill or similar mixer, of a compound of reduced nitrogen such as urea with a compound of Fe (II) stable as ferrous sulfate monohydrate, having free acidity will produce a melt of the urea by the formation of MCDS (monocarbamide dihydrogen sulfate) and DCDS (dicarbamide dihydrogen sulfate).
  • a compound of reduced nitrogen such as urea
  • Fe (II) stable as ferrous sulfate monohydrate having free acidity
  • magnesium either dolomite, calcined dolomite, magnesium hydroxide or magnesium oxide
  • dolomite either dolomite, calcined dolomite, magnesium hydroxide or magnesium oxide
  • magnesium sulfate is obtained, which is capable of capturing hydration water, therefore stabilizes the fertilizer before any hygroscopic phenomenon.
  • ammonium phosphate, TSP, SSP, phosphate rock, potassium chloride and potassium sulfate are added in the granulator.
  • the final fertilizer obtained has the following composition:
  • the nitrification process is inhibited due to the presence of the SAFH compound, which competes with the oxygen in the soil, therefore this compound captures the oxygen thus avoiding the presence of massive nitrates and nitrites, This compound thus ensures the permanence of in the soil of the ammoniacal form for a longer time.
  • the fertilizer formed must have a certain acidic character so that iron oxidation is gradual, and also to favor the presence of MCDS and DCDS, thus ensuring a dual effect on the action of the urease enzyme and the bacteria involved in nitrification.
  • Figure 1 shows a scheme of the fertilizer manufacturing process
  • the manufacturing was carried out during 15 hours of uninterrupted operation at an approximate flow of final product of 20 ton / hr, with a recycle / final product ratio of 2 to 1. 300 tons of final product were obtained.
  • the dosage of raw materials was as follows: Raw Material Weight percentage
  • the pug-mill (1) was fed at a rate of 6.5 ton / hr urea together with a flow rate of 1.8 ton / hr of the byproduct of the production of TiO ⁇ , iron sulfate monohydrate, which has the following composition:
  • the final product goes to the primary cooler (4) where its temperature is lowered from 50 ° C to 40 ° C, hardening the product by crystallization of the salts and leading then the product to the screens (5) of the final product, where there is physical separation of the commercial product from the recycle that feeds the granulator again, through the recycle line (8).
  • the final product is cooled again and conditioned in the conditioner (6) with paraffinic oils to prevent caking and is left ready for shipment, in the final store (2).
  • the final product gives the following final composition: Parameters Result (% by weight)
  • iron sulfate II is provided in the form of a coating.
  • a complex fertilizer is obtained.
  • the manufacturing facility was the same as for the previous example, however the process conditions changed, in this case other raw materials were introduced in addition to the nitrogenous ones, when introducing into the potassium formulation, recycling in manufacturing is increased , so the production rate decreases.
  • the manufacturing was carried out during 20 hours of uninterrupted operation at an approximate flow of final product of 15 ton / hr, with a recycle / final product ratio of 3 to 1. Approximately 300 tons of final product were obtained.
  • the dosage of raw materials was as follows:
  • the pug-mill (1) was fed at a rate similar to that of the previous example 6.5 ton / hr urea together with a flow rate of 1.8 ton / hr of the byproduct of the production of

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

Cette invention concerne un procédé permettant d'obtenir des engrais azotés, ainsi que des complexes et des engrais ainsi obtenus, lesquels contiennent un inhibiteur de la nitrification. L'inhibiteur contient, en tant que principe actif, un cation réducteur, plus précisément du fer II provenant des sous-produits de l'industrie du titane.
PCT/ES2006/070055 2006-05-11 2006-05-11 Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus WO2007132032A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES06743493T ES2398234T3 (es) 2006-05-11 2006-05-11 Procedimientos para la obtención de fertilizantes nitrogenados y complejos y fertilizantes así obtenidos
PCT/ES2006/070055 WO2007132032A1 (fr) 2006-05-11 2006-05-11 Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus
EP06743493A EP2017242B1 (fr) 2006-05-11 2006-05-11 Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2006/070055 WO2007132032A1 (fr) 2006-05-11 2006-05-11 Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus

Publications (1)

Publication Number Publication Date
WO2007132032A1 true WO2007132032A1 (fr) 2007-11-22

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PCT/ES2006/070055 WO2007132032A1 (fr) 2006-05-11 2006-05-11 Procédés permettant d'obtenir des engrais azotés et complexes et engrais ainsi obtenus

Country Status (3)

Country Link
EP (1) EP2017242B1 (fr)
ES (1) ES2398234T3 (fr)
WO (1) WO2007132032A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013135919A1 (fr) 2012-03-15 2013-09-19 Fertinagro Nutrientes, S.L. Procédé de traitement de matières protéiques, produit obtenu au moyen d'un tel procédé, et son utilisation en tant que fertilisant
WO2017009502A1 (fr) 2015-07-10 2017-01-19 Ampudia Soria José Francisco Nouvelle utilisation de l'urée sulfate
EP3130578A1 (fr) 2015-08-14 2017-02-15 Fertinagro Nutrientes, S.L. Composition fertilisante qui comprend un inhibiteur de l'activité uréase
WO2023135341A1 (fr) 2022-01-12 2023-07-20 Fertinagro Biotech, S.L. Composition inhibitrice de l'uréase et son utilisation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT5974B (lt) * 2013-01-31 2013-11-25 UAB "ARVI" ir ko Sudėtinių trąšų gavimo būdas
ES2569541B1 (es) * 2014-11-11 2017-02-21 Fertisierra, S.L.L. Fertilizante nitrogenado

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1060182A (en) * 1965-01-28 1967-03-01 Ici Ltd Improvements in and relating to fertilizers
GB1134465A (en) * 1966-08-16 1968-11-27 American Can Co Improvements relating to plant growth media and methods of making the same
GB1259778A (en) * 1968-04-27 1972-01-12 Fisons Ltd Chemical process
US4058389A (en) * 1974-12-20 1977-11-15 Societa' Italiana Resine S.I.R. S.P.A. Process for the preparation of fertilizers and soil modifiers
US5514201A (en) * 1991-06-13 1996-05-07 Tioxide Europe, S.A. Microelement deficiency corrector for farmland and process for preparation thereof
WO1996027571A1 (fr) * 1995-03-06 1996-09-12 Agrium Inc. Engrais contenant du soufre et son procede de production
EP1595860A2 (fr) * 2004-05-13 2005-11-16 DUSLO, a.s. Procédé de prèparation d'engrais,sous forme de granules, à base de nitrate et sulfate d'ammonium

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1060182A (en) * 1965-01-28 1967-03-01 Ici Ltd Improvements in and relating to fertilizers
GB1134465A (en) * 1966-08-16 1968-11-27 American Can Co Improvements relating to plant growth media and methods of making the same
GB1259778A (en) * 1968-04-27 1972-01-12 Fisons Ltd Chemical process
US4058389A (en) * 1974-12-20 1977-11-15 Societa' Italiana Resine S.I.R. S.P.A. Process for the preparation of fertilizers and soil modifiers
US5514201A (en) * 1991-06-13 1996-05-07 Tioxide Europe, S.A. Microelement deficiency corrector for farmland and process for preparation thereof
WO1996027571A1 (fr) * 1995-03-06 1996-09-12 Agrium Inc. Engrais contenant du soufre et son procede de production
EP1595860A2 (fr) * 2004-05-13 2005-11-16 DUSLO, a.s. Procédé de prèparation d'engrais,sous forme de granules, à base de nitrate et sulfate d'ammonium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013135919A1 (fr) 2012-03-15 2013-09-19 Fertinagro Nutrientes, S.L. Procédé de traitement de matières protéiques, produit obtenu au moyen d'un tel procédé, et son utilisation en tant que fertilisant
WO2017009502A1 (fr) 2015-07-10 2017-01-19 Ampudia Soria José Francisco Nouvelle utilisation de l'urée sulfate
EP3130578A1 (fr) 2015-08-14 2017-02-15 Fertinagro Nutrientes, S.L. Composition fertilisante qui comprend un inhibiteur de l'activité uréase
WO2017029421A1 (fr) 2015-08-14 2017-02-23 Fertinagro Nutrientes, S.L. Composition fertilisante incluant un inhibiteur de l'activité uréase
WO2023135341A1 (fr) 2022-01-12 2023-07-20 Fertinagro Biotech, S.L. Composition inhibitrice de l'uréase et son utilisation

Also Published As

Publication number Publication date
EP2017242A1 (fr) 2009-01-21
ES2398234T3 (es) 2013-03-14
EP2017242B1 (fr) 2012-12-26

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